Introduction and Importance

 Galvanization is a process of coating zinc on the surface of steel or iron.

 Hot-dip galvanization is a form of galvanization i.e. coating iron and
steel with zinc, which alloys with the surface of the base metal when
immersing the metal in a bath of molten zinc at a temperature of around
449°C.
 Mostly zinc is used as coating metal known as galvanizing and
occationally aluminium is used and it is called aluminizing.

 Pure zinc(Zn) react with oxigen and form zinc hydroxide(Zn(OH)2) again
further react with CO2 to form zinc carbonate(ZnCO3) which is very
strong.
 Examples in real life are Galvanized Steel pipes,hand rails,automotive
body parts etc.
 History
 In 1742, French chemist Paul Jacques Malouin described a method of
coating iron by dipping it in molten zinc in a presentation to the French
Royal Academy.
 In 1772 Luigi Galvani (Italy), galvanizing's namesake,discovered the
electrochemical process that takes place between metals during an
experiment with frog legs.
 In 1801 Alessandro Volta furthered the research on galvanizing when he
discovered the electro-potential between two metals, creating a
corrosion cell.
 In 1836, French chemist Stanislas Sorel obtained a patent for a method
of coating iron with zinc, after first cleaning it with 9% sulfuric acid (H
2SO4) and fluxing it with ammonium chloride (NH 4Cl).
 Process of coating
 There are a series of steps in order to coat the metal depending upon
the manufacturing process.They are
1.Metal surface preparation or Pre-treatment
2.Fluxing
3.Continuous Anneling
4.Immersion in metal bath
5.Post-treatment
 Metal surface preparation or Pre-treatment

 As the hot-dip coating process includes continuous annealing prior to

hot-dipping, interactions between the steel and the annealing
atmosphere occur resulting, for instance, in selective oxidation of the
alloying elements(Cr,Mn,Si and B etc.).
 The passive oxides on the steel surface decreases reactive wetting
between metallic iron and the galvanizing or aluminizing bath.
 Thus, the occurrence of coating defects (for example bare spots,
uncoated areas, degraded coating adhesion) bases in many cases on
selective oxidation on the external steel surface.
 Although the annealing atmosphere in modern continuous hot-dip
galvanizing lines(CGL) consists of ~5 to 10 vol.% of hydrogen
balanced in nitrogen, the oxygen partial pressure in the furnace is
under typical industrial conditions not low enough to avoid selective
oxidation completely.
 Metal surface preparation or Pre-treatment

 pre-treatment should be carried out in order to avoid external selective

oxidation of steel.
 Pre-treatment can be further divided into off-line and on-line pre-
treatments.
 Off-line pre-treatment:
a.Degreasing or rinsing
b. PVD or CVD(Physical or Chemical Vapour Deposition)
c. Pickling
d.Pre coating(Flash coating)
 Metal surface preparation or Pre-treatment

 On-line pre-treatment:-
Internal Oxidation
Bright Annealing
Nitrating
Oxidation/reduction method(pre oxidation)
 Reactive wetting:
Reactive wetting is a subset of the heavily studied
phenomenon of wetting, a process in which a liquid displaces another
fluid on a solid substrate.
 Adhesion:
The force of attraction between two dissimilar molecules or
atoms known as ”adhesion”.
 Process of coating

 Off-line pre-treatment:
It characteristically reveal the pre-treatment of steel
surface before processing the strip in CGL(continuous hot-dip
galvanizing lines).
 Metal surface preparation:-
 When steel delivered for galvanizing it may have grease or oil.
 It is usually removed in a degreaser or aqueous alkaline(caustic
solution) or acidic degreasing agents are employed.
 After degreasing the steel fabrication is washed in a water bath to
avoid tranfer of degreasing solvent to the next stage.
 In a degreasing step 2, a degreasing agent With a pH value of 7 to 14
and a specific gravity of 1.04 to 1.09 is used for the degreasing
process conducted at a temperature of 85° C.
 Pre-coating(Flash coating):

 Pre-coating(Flash coating):
Many pre treatment processings have been discussed
describing to avoid steel surface to avoid or hinder selective ox-
idation at the external surface during continuous annealing in a
CGL(continuous hot-dip galvanizing lines).
 One suggestion is to electrolytically depositing a thin layer of <1.0 μm
in thickness called ”flash coating”.
 For instane a nickel flash is confirmed to improve reactive wetting
and coating adhesion when hot-dip galvanizing of AHSS(Advanced
High Strength Steels).
 Because Nickel having a low affinity towards oxygen and forms Ni-
Al or Ni-Zn(-Al) intermetallics.
 At the same time, the pre-applied nickel flash on the steel surface
extends diffusion paths for less-noble alloying elements in the steel
substrate.
 Pre-coating(Flash coating)

 Flash coating could actually be performed in-line in a CGL, if

electrolytic cells are installed before the furnace.
 However, even modern CGLs are not equipped with an electrolytic
cell.
 Thus, industrial flash coating would have considerable cost as well as
process disadvantages and is therefore not used in the industrial
production of hot-dip coated AHSS (in Europe).
 CVD or PVD
 An innovative variation of pre-coating represents chemical or physical
vapor deposition (CVD/ PVD).
 Hereby, thin metallic or even oxidic pre-coating of ≤0.1 μm in
thickness can be applied.
 For instance, an aluminum layer applied by PVD on high manganese
alloyed AHSS.
 pre-coating AHSS with an oxide layer system in this case, an inner
oxide layer is supposed to act as diffusion barrier and to protect the
steel substrate against selective oxidation.
 The outer layer of iron oxide (FeO) can be reduced to metallic iron
during continuous annealing, which participates to reactive wetting
during hot-dipping.
 However, innovative pre-coatings applied by CVD or PVD are
currently limited at laboratory scale.
 Pickling
 Pickling:
Pickling is a metal surface treatment used to remove
impurities, such as stains,inorganic contaminants, rust or scale from
ferrous metals, copper, precious metals and aluminum alloys.
 A solution called pickle liquor, which contains strong acids, is used to
remove the surface impurities.
 The primary acid used is hydrochloric acid, and it is more expensive
than sulfuric acid, but it pickles much faster while minimizing base
metal loss.
 Pickling represents a more conventional alternative to aforementioned
pre-coating and is already used as process step in industrial hot-dip
coating.
 Carbon steels, with an alloy content less than or equal to 6%, are often
pickled in hydrochloric or sulfuric acid.
 Steels with an alloy content > 6% must be pickled in two steps and
other acids are used, such as phosphoric, nitric and hydrofluoric acid.
 Rust and acid resistant chromium-nickel steels are pickled in a bath of
hydrochloric and nitric acid.
 Sheet steel that undergoes acid pickling will oxidize (rust) when
exposed to atmospheric conditions of moderately high humidity so a
thin film of oil or similar waterproof coating is applied to avoid it.
 This must later be removed for many fabrication, plating or painting.
 Advantages:
 As the less-noble alloying elements will not form new oxides during
the low-temperature heat treatment prior to hot-dipping, reactive
wetting can be clearly improved compared to conventional continuous
hot-dip coating without pickling.
 Disadvantages:
 it is difficult to handle because of its corrosiveness.
 It is not applicable to all steels.
 Hydrogen embrittlement becomes a problem for some alloys and
high-carbon steels.
 The hydrogen from the acid reacts with the surface and makes it
brittle and causes cracks.
 Because of its high reactance to treatable steels, acid concentrations
and solution temperatures must be kept under control.
 if cold-rolled strips are considered, the pickling approach will have
clear cost disadvantages, because recrystallization annealing as off-
line pre-treatment needs an expanded production path.
 On-line pre-treatment

 In-line conditioning of surface:

An approach with in-line treatment includes a specifical
modification of the steel surface during continuous annealing, what is
typically carried out by modifying the gas/metal reaction.
 Processing approaches with off-line pre-treatments are associated with
higher production costs, because additional processing steps are
necessary before subjecting to a CGL.
 In this context, in-line conditioning of the steel surface means
exposing the strip to a gas/metal reaction, which is specifically
modified to avoid external oxidation of less-noble alloying elements
during annealing.
 For this, it is crucial to control oxygen partial pressure by varying
hydrogen and dewpoint of the annealing atmosphere.
 Internal oxidation

 Internal oxidation:
Internal oxidation means that the flux of ad/absorbed
oxygen inwards the steel substrates dominates the flux of oxidizing
alloying elements towards the steel surface.
 Thus, selective oxidation appears internally within the sub-
surface(close beneath the steel surface with in micrometers) of the
steel.
 Wagner model states that this external oxidation can be hampered
kinetically, if the oxidation potential of the annealing atmosphere is
high enough to promote internal oxidation of alloying elements.
 a controlled increase of the oxygen partial pressure or the
dewpoint( H2O/H2 ratio) of the annealing atmosphere will favour the
internal oxidation.
 This can be realized by a controlled and regulated injection of oxygen
or water into the hydrogen-nitrogen mixture within the furnace and/or
lowering the hydrogen fraction of the annealing atmosphere.
 if the dewpoint during continuous annealing is increased, internal
oxidation increases accompanied by improved coating quality.
 However, the steel substrate tends to decarburization with increasing
dewpoint of the annealing atmosphere.
 The injection of controlled amounts of carbon oxide (CO) and carbon
dioxide (CO2) into the annealing atmosphere to promote internal
oxidation of alloying elements.
 However, the presence of CO and CO2 in the annealing atmosphere
can be accompanied by uncontrolled carburization of steel bulk.
 Bright annealing

 internal oxidation of the less noble alloying elements means hindering

their external oxidation kinetically.
 In contrast, the bright annealing process approach describes the
increase of the reduction potential of the annealing conditions in order
to avoid oxidation thermodynamically.
 Following the Richardson-Ellingham diagram, reduction potential of
the annealing conditions will increase, if the oxygen partial pressure
and the H2/H2O ratio (→ dewpoint) of the annealing atmosphere
decrease while keeping the annealing temperature constant and
viceversa.
 To illustrate this, bright annealing was successfully used at laboratory
scale even to hot-dip galvanize high manganese alloyed TWIP steel
alloyed with >20 wt.% of manganese.
 Unfortunately, annealing conditions necessary to effectively bright
annealing are far away from process parameters used in industrial
CGLs.
 Realizing and maintaining a (super) low dewpoint is very difficult in a
heavy duty continuous annealing furnace.
 Furthermore, if the annealing temperature is increased, coarse grain
microstructure could appear in the steel substrate degrading
mechanical properties.
 Increasing the hydrogen amount in the annealing atmosphere to a
value up to 100 vol.% could still be an option, but safety standards
such as technical feasibility,safety and energy efficiency must be
considered.
 Nitrating

 Nitrating:
Nitrating of the sub-surface was suggested by exposing the steel
to an annealing atmosphere,which includes up to ~5 vol.% of
ammonia(NH3) aside hydrogen and nitrogen.
 The positive effect of this nitrating approach bases on diffusion of
ad-/absorbed nitrogen inwards the sub-surface, where it forms
intermetallic nitrates (AlN, BN, Fe3N) with the alloying elements and
iron of the matrix.
 As this nitrate formation preferably appears on crystal defects in the
matrix such as grain and phase boundaries, decreases diffusion paths.
 Additionally, the nitrate formation increases the number of nucleation
points for recrystallization resulting in a local grain refinement within
the sub-surface.Thus, no. of possible diffusion directions and paths are
increased, decreasing the material flow to the surface.
 In comparison to other processing approaches nitrating could be
realized easily in a CGL by injecting ammonia in addition to
hydrogen and nitrogen into the annealing atmosphere.
 Limitations:
 However, safety standards must be considered by handling with
ammonia.
 Furthermore, effectiveness of nitrating decreases with decreasing
amount of nitrogen-affine alloying elements – of aluminum in
particular – in the steel composition.
 The danger of embrittlement of structural components of the
annealing furnace limits the use of the nitrating approach additionally.
 Oxidation/reduction method
(Pre-oxidation)
 Oxidation/reduction method(Pre-oxidation):
 The oxidation/reduction method – so-called pre-oxidation – is known
to the operator of a CGL for decades and the industrial usage of pre-
oxidation has been reported on since the 1960s.
 The pre-oxidation approach fundamentally bases on the initial
generation of a covering iron oxide layer on the steel surface blocking
off all diffusion of less noble alloying elements and oxygen.
 This iron oxide layer can be re-reduced to metallic iron during
soaking the strip at annealing temperature in H2-N2 under normal
industrial conditions (reduction step).
 Thus, reactive wetting and coating quality can be considerably
improved compared to a conventional annealing treatment.
 The iron oxide layer must be continuous and thick enough to hamper
selective oxidation of less-noble alloying elements effectively.
 if iron oxide layer thickness is too high (~ > 200-300 nm) it cannot
completely reduced to iron.
 Pre oxidation can be done based on heating sections in industrial
CGLs.They are DFF,RTF,DFI.
 DFF(Direct Fired Furnace) type heating section :
Adjusting the air/fuel gas ratio (so called λ value) of
the open burners to >1.0 causing an excessive amount of oxygen
within the DFF section
 RTF(Radiant Tubular Furnace) type heating section:
Implementation of a separated reaction chamber
(so-called “oxidation chamber”), in which a controlled oxygen
containing atmosphere exists.
 DFI(Direct Flame Impengement ) type heating section:
Adjusting the λ value of the open DFI boosters
to >1.0 in a similar manner as using a DFF-type heating section.
 Today, pre-oxidation in CGLs equipped with DFF- and RTF-type
heating sections represents a key technology to hot-dip galvanize or
aluminize modern AHSS for both hot and cold sheet metal forming.
 pre-oxidation could also an appropriate processing approach even to
hot-dip galvanize TWIP steel alloyed with >20 wt.% of manganese.
 In the case of pre-oxidizing such high-manganese AHSS, a covering
(Mn,Fe)O mix-oxide layer results from the oxidation step instead of
the expected iron oxide layer.
 During reductive annealing this (Mn,Fe)O layer transforms to a
manganese oxide layer with embedded metallic iron
( MnO.Fe(metall) layer).
 Fluxing
 After pre-treatment steel strip coated or immersed in solution
containing flux.
 This will protect the steel to avoid contact with air and gives good
adherence and reactive wetting.
 Often zinc ammonium chloride is used as fluxing agent to avoid
oxidation of steel strip.
 It is allowed to dry on steel which aids the process of adhesion and
reactive wetting.
 Other fluxing agents such as zinc chloride and aluminium chloride also
used at specified temperature.
 Hot dip galvanizing

 It is the process step in which specially prepared steel strip heat

treated prior to immersion in the zinc or aluminium bath if required.
 Temperature of approximately 450°C and 700°C need to be
maintained (bath temperature) for galvanizing (zinc coating) and
aluminum coating respectively.
 The conventional zinc bath consists of zinc (99.3 wt. % Zn)
containing also Al, Bi, Fe, Ni, Sn, Pb at the temperature ranging from
450℃ to 560℃.
 Lead is often added to the molten zinc bath to improve the fluidity of
the bath (thus limiting excess zinc and by improved drainage
properties), helps prevent floating dross, makes dross recycling easier
and protects the Pilling kettle from uneven heat distribution from the
burners.
 hot-dip galvanizing

 In a conventional hot-dip galvanizing anti-corrosion process, an

object coated With a fusing agent is dipped into a zinc solution at
450° C. to 520° C.
 In general, a conventional zinc solutionis composed of 96.4% zinc,
0.01% aluminum, 1.45% lead, 0.15% chromium and 1.95% of other
element measured by Weight.
 To control the surface condition of a galvanized zinc layer, aluminum
is added in a melted zinc solution, and lead is added to retard the rate
of heat dissipation.
 A layer of dross Will be formed on the surface of the melted zinc
solution When the zinc solution is oxidized or When zinc and iron are
hot-dip galvanized.
 Hot-Dipped Galvanized

Zn Pb Fe Cd
98-99.9 0.003-1.6 0.003-.05 0.003-.5

Al Sb Sn
0.1-.25 0.01 0.3-1.5
Increased Coating Aids in Wetting Frosted Spangle
Adherence,
Passive Layer

Zinc
Aluminum Oxide Passive Layer
Zinc Layer Thickness
steel
0.13 to 1.2 oz/sq ft
0.0002 to 0.0015 in.
 The time period upto which steel strip immersed in zinc bath vary
from specimen to specimen based on thickness and
complexity.Generally it takes five minutes.
 When clean steel or iron dipped into the bath a series zinc-iron ally
layers formed due to the reaction between iron and zinc.
 The rate of reaction between the zinc and iron is parabolic with time
so initial rate of rection is very rapid and considarable agitation can be
observed compared to the latter.
 The main thichness of coating is formed during this period.
 Subsequently,reaction slows down and coating thickness is not
increased significantly even if the article immersed for a long period
of time.
 The steel strip immersed untill it will attain equilibrium with zinc
bath.
 Post treatment

 Post treatment can include quenching into water or air cooling.

 Conditions in the galvanized plant such that temperature,humidity and
air quality doesn't affect the quality of the galvanizing coating.In
contrast to the painting.
 Excess coating thickness can be adjusted by blowing hot air.
 The thickness of coatings was determined by electromagnetic
thickness gauge(Dualscope MP0).

 galvanizing
 The process of hot-dip galvanizing results in a metallurgical bond
between zinc and steel with a series of distinct iron-zinc alloys. The
resulting coated steel can be used in much the same way as uncoated.
 A typical hot-dip galvanizing line operates as follows:-
 Steel is cleaned using a caustic solution. This removes oil/grease, dirt, and
paint.
 The caustic cleaning solution is rinsed off.
 The steel is pickled in an acidic solution to remove mill scale.
 The pickling solution is rinsed off.
 A flux, often zinc ammonium chloride is applied to the steel to inhibit
oxidation of the cleaned surface upon exposure to air. The flux is allowed
to dry on the steel and aids in the process of the liquid zinc wetting and
adhering to the steel.
 Advantages
 Galvanized steel is widely used in applications where corrosion resistance
is needed without the cost of stainless steel, and is considered superior in
terms of cost and life-cycle.
 It can be identified by the crystallization patterning on the surface (often
called a "spangle").
 Galvanized steel can be welded; however, one must exercise caution
around the resulting toxic zinc fumes.
 Galvanized steel is suitable for high-temperature applications of up to 392
°F (200°C). The use of galvanizedsteel at temperatures above this will
result in peeling of the zinc at the inter metallic layer.
 Advantages
 Electrogalvanized sheet steel is often used in automotive manufacturing to
enhance the corrosion performance of exterior body panels; this is,
however, a completely different process which tends to achieve lower
coating thicknesses of zinc.
 Like other corrosion protection systems, galvanizing protects steel by acting
as a barrier between steel and the atmosphere.However, zinc is a more
electropositive (active) metal in comparison to steel.
 This is a unique characteristic for galvanizing, which means that when a
galvanized coating is damaged and steel is exposed to the atmosphere, zinc
can continue to protect steel through galvanic corrosion.
 Applications
 Hot-dip galvanized steel strip (also sometimes loosely referred to as
galvanized iron) is extensively used for applications requiring the strength
of steel combined with the resistance to corrosion of zinc.
 Roofing and walling, safety barriers, handrails.
 Consumer appliances and automotive body parts.
 Commonly used is in metal pails and also used in most heating and
cooling duct systems in buildings.
 Benefits
 Most economic friendly finishing process to prevent corrosion.
 Highly sustainable and produce minimal waste i.e uncoated zinc
remains in bath for re-use.
 Recyclable without loss of chemical or mechanical properties
due to metal's non-ferrous properties.
 Galvanized products, once installed can also removed,re-
galvanized and reused,as well as easily recycled with steel
scrap in the steel production process.
 Durability – a permanently bonded tough coating.
 Hygienic – easy to clean surface.
 Long life – upto 50 years and maintenance free.
 Economic – lowest overall cost compared to any other
coatings.
 Specifications
 A hot-dip galvanized coating is relatively easier and cheaper to specify
than an organic paint coating of equivalent corrosion protection
performance.
 The British, European and International standard for hot-dip galvanizing
is BS EN ISO 1461 which specifies a minimum coating thickness to be
applied to steel in relation to the steels section thickness e.g. a steel
fabrication with a section size thicker than 6 mm shall have a minimum
galvanized coating thickness of 85 μm.
 Further performance and design information for galvanizing can be found
in BS EN ISO 14713-1 and BSEN ISO 14713-2.
 Why to galvanize the steel

 Maintenance free
 Effactive coating
 It's sustainable
 It's tough
 It's fast
 It is self healing
 Offers complete coverage
Conclusion
 Lead free galvanizing

 In a lead-free hot-dip galvanizing method a special high grade (SHG)

zinc tablet With a 99.995% purity is used and zinc solution contain 98
to 99% Zn and 0.2 to 1.0%Al measured by weight.
 trace element is one selected from the collection of molybdenum,
bismuth, silver, titanium and nickel.
